Substituted 1,4,5-triamino-8-hydroxy-anthraquinone dyes

ABSTRACT

1,4,5-TRIAMINO-8-HYDROXY ANTHRAQUINONE DYESTUFFS FOR POLYESTERS AND POLYAMIDES CONTAINING SUBSTITUTED 2 AND/OR 3 POSITIONS WHEREIN ONE OF SAID POSITIONS CONTAINS A SUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF SUBSTITUTED OR UNSUBSTITUTED ALKYL, ARYL, AND ARALKYL GROUPS LINKED TO THE ANTHROQUINONE NUCLEUS THROUGH A BRIDGE SELECTED FROM THE GROUP CONSISTING OF O, S, SO, AND SO2, ARE PREPARED BY REACTING A CYCLIC SULFAMIDE OR CYCLIC SULFIMIDE ESTER WITH SULPHUR IN OLEUM.

United States Patent 3,557,154 SUBSTITUTED 1,4,5-TRIAMlN0-8-HYDROXY-ANTHRAQUINONE DYES Rutger Neefi and Wilhelm Gohrbandt, Leverkusen, and

Robert Kuth, Cologue-Muengersdorf, Germany, assignors to FarbenfabrikenBayer Aktiengesellschaft, Leverkusen, Germany, a corporation of GermanyNo Drawing. Continuation-impart of application Ser. No. 444,026, Mar.30, 1965. This application July 29, 1966, Ser. No. 568,740

Claims priority, application Germany, Aug. 7, 1965,

46,842 Int. Cl. C09h 1/50, l/52, 1/56' US. Cl. 260373 Claims ABSTRACT OFTHE DISCLOSURE 1,4,5-triamino-8-hydroxy anthraquinone dyestuffs forpolyesters and polya-rnides containing substituted 2 and/ or 3 positionwherein one of said positions contains a substituent selected from thegroup consisting of substituted or unsubstituted alkyl, aryl, andaralkyl groups linked to the anthroquinone nucleus through a bridgeselected from the group consisting of O, S, SO, and S0 are prepared byreacting a cyclic sulfamide or cyclic sulfimide ester with sulphur inoleum.

This application is a continuation-in-part of our copending application,Ser. No. 444,026, filed Mar. 30, 1965, for New Dyestuffs.

It has been found that substituted 1.4.5-triamino-8-hydroXy-anthraquinone' dyes are obtained when cyclic sulphamide estersof Formula I or cyclic sulphimide esters of Formua II S02 i l X-R be O2I1' I 0 N are reacted with sulphur in oleum. In Formulae I and H, Xstands for an -O--, -S, SO or -SO group, R for an alkyl, aralkyl or arylradical which may optionally bear further substituents, R for hydrogen,halogen or SR-, SOR, SO R"- or OR" groups and R" for unsubstituted orsubstituted alkyl, aralkyl or aryl radicals.

The dyes obtained by the process according to the invention can bedescribed by the following Formula 3,557,154 Patented Jan. 19, 1971 III,wherein X, R and R have the meaning stated above.

no l rHz which may themselves be substituted by halogen, alkoxy(preferably low alkoxy), cyano or carboxyalkyl radicals, or optionallyfurther substituted phenyl or phenoxy groups, (possibly esterified)carboxy groups, trifluoromethyl or acetyl groups, amino groups which maypossibly be substituted by one or two (possibly substituted) alkyl(preferably low alkyl) or phenyl radicals.

If the radicals R and R" are aralkyl radicals, preferably suitable arebenzyl or naphthylmethyl radicals, which may be substituted by halogensor alkyl groups. If the radicals R and R in the above formulae stand foralkyl radicals, there are to be mentioned in particular those with l-16carbon atoms, it being possible that the alkyl radicals may besubstituted, e.g. by halogen atoms, alkoxy, alkoxyalkyleneoxy, cyano or(possibly esterified) carboXy groups or by amine groups which maypossibly be substituted by one or two alkyl, alkoxyalkyl, cyanoalkyl orphenyl radicals.

Examples of the anthraquinone sulphamide esters used as startingmaterial are the following: adducts of cyclicS-nitro-anthraquinone-1,4-disulphonimide with benzenesulphinic acid,4-chlor0-, 3-bromoor 3-fluorobenzenesulphinic acid, 4-methyl-, 4-ethyl-,4-isopropyl-, 4-butylor 4-amyl-benzenesulphinic acid,3-trifiuoromethyl-benzenesulphinic acid, 4-methoxy, ethoxyorbutoxy-methylbenzenesulphinic acid, 4-methoxyor4-ethoxy-ethyl-benzenesulphinic acid, 4-,8-chloroor-cyanoethyl-benzenesulphinic acid, 3-carboethoXy-benzenesulphinic acid,4 ethoxycarbonylmethyl-benzenesulphinic acid, 4-phenylor4-phenoxy-beuzenesulphinic acid, 3-acetyl-benzenesulphinic acid,4-aminoor 4-dimethylarnino-benzenesulphinic acid, 4-phen'ylamino-benzenesulphinic acid, 2,5-dichlorobenzenesulphinic acid,2,4-dimethyl-benzenesulphinic acid, ocand ,B-naphthalenesulphinic acid,benzylsulphinic acid, 4- chlorobenzylsulphinic acid, 00- andB-naphthylmethanesulphinic acid, methanesulphinic acid, chlor0-,dichloroor trichloromethane-sulphinic acid, ethane-, propane-, butane-,pentane-, heXane-, octane-, dodecaneor hexadecanesulphinic acid,Z-chloroethaneor 4-chloro-butanesulphinic acid, 2-methoxyor2-ethoxyethane-sulphinic acid, 2-(w-methoxyor-ethoxyethyleneoxy)-ethanesulphinic acid, 2-cyanoethanesulphinic acid,ethoxycarbonylmethanesulphinic acid, methoXy carbonylmethanesulphinicacid, Z-dimethyland 2-diethyl-aminoethanesulphinic acid,Q-bis-methoxyethyland 2-bis-cyanoethylethanesulphinic acid, further theadducts of cyclic S-nitro- 2- and/or-3-bromo-anthraquinone-1,4-disulphonimide, of cyclic 5-nitro-2- and/ or-3-chloro-anthraquinone-1,4-disu1- p'honimide, of cyclic 5-nitro-2-and/or -3-methylthioanthraquinone-l,4-disulphonimide, of cyclicS-nitro-Z- and/ or -3-phenyl-thio-anthraquinonel ,4-disulphonimide, ofcyclic 5-nitro-2- and/or-3-methylsulphoxido-anthraquinone-1,4-disulphonirnide, of cyclic5-nitro-2- and/or -3-phenylsulphoxido-anthraquinone-1,4-disulphonimide,of cyclic 5-nitro-2- and/or -3-methylsulphonyl-anthraquinone-1,4-disulphonimide, of cyclic S-nitro-Z- and/or -3-p'henylsulphonyl-anthraquinone-1,4-disulphonimide, of cyclic 5-nitro-2-and/or 3 (4' chloro) phenylsulphonylanthraquinone-l,4-disulphonimide orof cyclic 5-nitro-2- and/ or -3-(4' methyl)phenylsulphonyl-anthraquinone- 1,4-disulphonimide with theabove-mentioned sulphinic acids.

Sulphamide esters suitable for the process according to the inventionare, furthermore, cyclic 5-nitro-2-methylthio-, benzylthio-, ethylthioor-phenylthio-anthraquinone- 1,4-disulphonamide, cyclic5-nitro-2,3-bis-(methylthioor-phenylthia)-anthraquinone-l,4-disulphonamide, cyclic 5-nitro-2-methylthioor -phenylthio 3 bromoanthraquinone-1,4-disulphonamide, cyclic 5-nitro-2-methylthioor-phenyltl1io3-chloro-anthraquinone-1,4 disulphonamide, cyclic5-nitro-2-methylsulphoxidoor-phenylsulphoxidoanthraquinone-l,4-disulphonamide, cyclic5-nitro-2-merhylsulphoxidoor -phenylsulphoxido-3-bromoor-chloroanthraquinone-l,4-disulphonamide, cyclic5-nitro-2,3-bismethylsulphoxidoor -phenylsulphoxido-anthraquinone-1,4-disulphonamide.

Further suitable starting compounds for the process according to theinvention are cyclic 5-nitro-2-methoxy-, -benzyloxyor-phenoxy-anthraquinone-1,4-disulphonamide, cyclic5-nitro-2,3-bis-(methoxyor -phenoxy)- anthraquinone-1,4-disulphonamide,cyclic 5-nitro-2-methoxyor-phenoxy-3-bromo-anthraquinone-1,4-disulphonamide, cyclic5-nitro-2-methoxyor -phenoxy-3-chloroanthraquinone-l,4-disulphonamide,cyclic 5-nitro-2-methoxyor -phenoxy-3-methylthioorphenylthio-anthraquinone-1,4-disulphonamide, cyclic 5-nitro-2-methoxyor-phenoxy-3-methylsulphinylor-phenylsulphinyl-anthraquinone-1,4-disulphonamide or cyclic5-nitro-2-methoxyor -phenoxy-3-methylsulphonylorphenylsulphonylanthraquinone-1,4-disulphonamicle.

As already mentioned, instead of the cyclic sulphamide esters, cyclicsulphimide esters may be used for the process according to theinvention, but it is more advantageous to use the cyclic sulphamideesters since the cyclic sulphimide esters have in most cases first to beprepared from the cyclic sulphamide esters by oxidation.

The process according to the invention may for example be carried out insuch a manner that the cyclic sulphamide esters or the cyclic sulphimideesters are treated at -l50 C., preferably 20l20 C., with a solution ofsulphur in 65% oleum, excess sulphur then precipitated by cautiousdilution with water and the reaction product isolated in known manner,e.g. by pasting of the solution on ice water. The sulphur is thereforeused preferably in amounts of approximately 1 mole sulphur or more, e.g.2 to 3 moles sulphur, per mole anthraquinone compound.

The dyes obtainable by the process according to the invention, ormixtures thereof, serve for the dyeing of natural fibers and syntheticmaterials, preferably polyamides, polyurethanes, polyacrylonitriles,polypropylene and polyesters, there being meant by polyesters lineararomatic polyesters in particular, such as polyethyleneterephthalate, orpolyesters of terephthalic acid and 1,4- bis-hydroxymethyl-cyclohexane,as well as cellulose esters, such as cellulose triacetate or cellulose-2/2-acetate. It is advantageous to bring the dyes into a finely dividedstate according to the customary methods, e.g. by reprecipitation,grinding or kneading in the presence of dispersing agents, and to usethem according to known dyeing methods. While cellulose-2 /z-acetate isdyed for example at 60-80 C, in the presence of Marseilles soap,cellulose triacetate fibres and polyamide fibres, can be dyed forexample at 100 C. In the dyeing of polyethyleneterephthalate fibres theusual dyeing accelerators may be added, or dyeing carried out at l20l45C. under pressure. Moreover, the dyes are ideally suited for the dyeingand printing of polyester or polyamide fibres according to the thermosolprocess in which the padded or printed fibre materials, optionally afteran intermediate drying, are heated for a short time to temperatures inthe range around 180220 C. The heating takes place generally for periodsof 30 seconds to 2 minutes.

The dyeings and prints obtained with the dyes according to the inventionare distinguished by clear shades and possess outstanding fastness tolight, washing, thermofixation and sublimation, with high dye yield andvery good build up.

In the following examples, parts are parts by weight unless otherwisestated.

EXAMPLE 1 (a) 11.1 parts flowers of sulphur are added at C., to amixture of 68 parts 65% oleum and 43 parts sulphuric acid monohydrate,the mixture stirred for minutes at 1520 C., and then diluted with 167parts sulphuric acid monohydrate. parts of a mixture of cyclic.5-nitro-2- and -3-(4'-chloro) phenylsulphonylanthraquinone 1.4disulphonamide are now introduced at l520 C., the mixture stirred for 2hours at 25-28" C., warmed to C., in 2 hours and heated to C., in 1hour. 67 parts 85% sulphuric acid are then added, the mixture heated toC., and after 5 minutes at 115 C., allowed to cool. It is then dilutedwith parts water, filtered olf from the precipitated sulphur withsuction, and the solution introduced into 1000 parts ice water. Afterfiltration of the reddish blue amorphous product with suction, washingwith water and drying, 28.2 parts of a dye mixture consisting of 1.4. 5triamino- 8 hydroxy 2 and -3 (4' chloro) phenylsulphonylanthraquinone(=92% of the theory) are obtained.

When, instead of the mixture of cyclic 5nitro-2- and -3-(4 chloro)phenyl anthraquinone 1.4 disulphonamide, equivalent amounts of thecorresponding 1.4-disulphonimide are used, the same end product isobtained Calculated for C H ClN O S (443.8) (percent): Cl, 8.01; O,18.05; S, 7.22. Found (percent): Cl, 7.89; O, 18.33; S, 7.64.

The mixture of cyclic 5-nitro-2- and -3-(4'-chloro)- phenylsulphonylanthraquinone 1.4 sulphonamide used as starting material can be preparedfor example as follows: 19.2 parts 80.4% sodiump-chlorobenZene-sulphinate are added, in 1-2 hours at 2025 C., to 240parts cyclic 5 nitroanthraquinone 1.4 disulphonimide in a mixture of1500 parts methanol and 44 parts 98% sulphuric acid. Stirring iscontinued for about 2 hours, the product which has crystallised inbeautiful yellow needles is filtered off with suction, washed with waterand, after drying, 310 parts of a mixture of cyclic 5- nitro 2 and-3-(4-chloro)-phenylsulphonylanthraquinone-1,4 disulphonamide (=90% ofthe theory) are obtained. Instead of in methanol, the reaction may alsobe carried out in other solvents such as water or glacial acetic acid,optionally with heating.

(b) A fabric consisting of polyethyleneterephthalate fibres isimpregnated on a padding mangle with a liquor which contains, per litre,20 g. of a mixture of 1.4.5- triamino 8 hydroxy 2- and -3-(4 chloro)phenyl sulphonyl anthraquinone and 10 g. of a thermosol auxiliary, inparticular a polyether such as is described for example in Belgianpatent specification No. 615,102. The fabric is then squeezed untilthere is a weight increase of 70% and dried in a suspension jet drier ordrying cabinet at 80l20 C. The fabric is then treated with hot air forabout 45 seconds at 2l0 C., in a stenter or jet hot flue after which itis rinsed, possibly subjected to a reductive after-treatment, washed,rinsed and dried. The reductive after-treatment for the purpose ofremoving the portion of dye adhering superficially to the fibres mayoccur in such a manner that the fabric is entered at 25 C., into aliquor containing 35 ccm./l. solution of caustic soda at 38 B6. and 1-2g./l. concentrated hydrosulphite, heated to 70 C., within about 15minutes and left at 70 C., for a further 10 minutes. It is then rinsedhot, acidified at 50 C., with 2-3 ccm./l. 85% formic acid, rinsed anddried. A clear, blue dyeing is obtained which, is distinguished by itshigh dye yield and very good build as well as by outstanding fastness tolight, thermofixation, washing, rubbing and sublimation. In similarmanner a clear, blue dyeing is obtained when, instead ofpolyethyleneterephthalate fibres, polyester fibres from 1.4-bis-hydroxymethylcyclohexane and terephthalic acid, or cellulosetriacetate fibres or polyamide fibres, are used.

(c) A pre-cleaned and therrnofixed fabric consisting ofpolyethyleneterephthalate fibres is printed with a printing paste whichconsists of the following components: 40 g. of a mixture of1.4.5-triamino-8-hydroxy-2- and -3-(4'-chloro)-phenylsulphonyl-anthraquinone, 475 g. water, 465 g. crystal gum1:2 and 20 g. sulphonated castor oil. Instead of crystal gum an alginatethickener may be used. In order to fix the dye, the printed and driedgoods are taken, at 190-210 C., over a high-performance stenter orthrough a condensation machine. The duration of treatment is 3060seconds. The fixed print obtained is then rinsed cold, soaped at 70-80C., for about 10 minutes with 12 g./l. anion-active washing agent, firsthotrinsed and then cold-rinsed, and dried. A print analogous to thedyeing of Example 1(b) is obtained which is distinguished by the sameoutstanding fastnesses. In similar manner a clear, blue print isobtained when, instead of polyethyleneterephthalate fibres, polyesterfibres from 1.4-bis-hydroxymethylcyclohexane and terephthalate acid, orcellulose triacetate fibres or polyamide fibres, are used.

(d) 10 parts by weight polyethyleneterephthalate fibres are dyed at125130 C., for 2 hours in a liquor adjusted to pH 4.5 and consisting of400 parts by Weight water and 0.1 part by weight of the finely disperseddye mentioned in Example 1(a), then rinsed and dried. A clear, bluedyeing distinguished by high fastnesses is obtained.

(e) 10 parts by weight polyethyleneterephthalate fibres are dyed at 100C., for 1.5 hours in a liquor adjusted to pH 4.5 and consisting of 400parts water, 0.1 part by weight of the finely dispersed dye mentioned inExample 1(a) and 1.5 parts by weight cresotic acid methyl ester. Aclear, blue dyeing characterised by very good fastnesses is obtained.

The dyes which are obtained from mixtures of cyclic 5-nitro-2- and-3-arylsulphonyl-anthraquinone-1.4-disulphonamides or-1.4-disulphonimides according to Exam- ;ple 1(a), and their shades onpolyethyleneterephthalate fibres, are given in the following table:

Example Dye mixture consisting of- Shade 2 1.4.5-triamin-8-hydroxy-2-and -3-phenylsulph0nyl- Blue.

anthraquinone.

3 1.4.5-triamino-8-hydroxy-2- and -3-(2-chloro)- Do.

phenylsulphonylanthraquinone.

4 1A.5triamino-8-hydroxy-2- and -3-(3-bron1o)- D0.

phenylsulphonyl-anthraquinone.

5 1.4.5-triamino-8-hydroxy-2- and -3-(3-fluoro)- D0.

phenylsulphonyl-antraquinone.

6- 1.4.5-triamino-8-hydroxy-2- and -3-(4-methyl)- D0.

phenylsulphonyl-anthraquinone.

7 1.4.5-triamino-8-hydroxy-2- and -3-(4-ethyl)- D0.

phenylsulphonyl-anthraquinone.

8 1.4.5-triamino-8-hydroxy2- and -3-(4-isobutyl)- D0.

phenylsulphonyl-antln'aquinone.

9. 1.4.5-triamino-8hydroxy-2- and -3- (3-trifiuoro- D0.

methyl)-phenylsulphonyl-anthraquinone.

10 1.4..5-triamin0-8-hydroxy-2- and -3-(4-methoxy- D0.

methyl)-phenylsulphonyl-anthraquinone.

11 1.4.5'triamin0-8-hyd1'0xy-2- and -3-(4-eth0xy- D0.

methyl)-pheny1sulphonyl-anthraquinone.

12 1.4.5-triamino-8-hydroxy-2- and -3-(4-B-meth0xy- D0.

ethyl)-phenylsulphonyl-anthra' uinone.

13- 1.4.5-triamino-8-hydroxy-2- and (4-cyano- D0.

methyl)-phenylsulphonyl-anthraquinone.

14 1.4.5-triamino-8-hydroxy-2- and -3-(4ethoxy- D0.

carbonylmethyl)-pheny1sulphonyl-anthraquinonc.

15- 1.4.5-triamino-8-hydroxy-2- and -3-(4-phenoxy)- D0.

phenylsulphonyl-anthraquinone.

16 1.4.5-trianiino-8-hydroxy-2- and -3-(3-eth0xy- D0. carbonyl)-phenylsulphonyl-anthraquinone.

1.4.5-triamin0-8-hydroxy-2- and -3- (4-methoxy- Do.

carbonyl)-phenylsulphonyl-anthraquinone.

18 1.4.5-triamin0-8-hydroxy-2- and -3-(4-amiu0) Do.

fhenylsulphonyl-authraquinone.

19 1. .5-triamiu0-8-hydroxy-2- and -3-.(4-dimethyl- Do.

amino)-phenylsulphonyl-anthraquinone.

20 1.4.5-trinmin0-8-hydroxy-2- and -3-(4-diethyl- D0.

amino)phenylsulphonyl anthraquinone.

21 1.4.5-triamino-8-hydroxy-2- and -3- (4-N-i3- Do.

bisrnethoxyethylamino)-phenylsulph0nylanthraquinone.

22 l.4.5-triamino-8-hydroxy-2- and -3- (4-N-B- D0.

biscyanoethylamino)-pheuylsulphonyl.

phenyl-anthraquinoue.

EXAMPLE 30 11.1 parts flowers of sulphur are added at 15-20" C., to amixture of 68 parts 65% oleum and 43 parts sulphuric acid monohydrate,the mixture stirred for 30 min utes at 1520 C., and then diluted with167 parts sulphuric acid mouohydrate. 37.6 parts cyclic 5-nitro-2-phenylsulphonyl anthraquinone 1.4 disulphonimide are now introduced at15-20 C., the mixture stirred for 2 hours at 2528 C., warmed to 60 C.,in 2 hours and heated to C., in 1 hour. 67 parts 85% sulphuric acid arethen added, the mixture heated to C., and after 5 minutes at 115 C.,allowed to cool. It is then diluted with parts water. filtered off fromprecipitated sulphur with suction and then water is added slowly untilthe reaction product has crystallised out in small orange-red needles.It is filtered off with suction and after washing with water and drying,25.4 parts 1.4.5-triamino 8 hydrox'y 2 phenylsulphonyl anthraquinone(=90.5% of the theory) are obtained in small blue needles.

Calculated for C H N O S (409.3) (percent): N, 10.27; 0, 19.55; S, 7.82.Found (percent): N, 10.02; 0, 19.87; S, 8.12.

Dyed or printed according to the processes of Example 1(b) or 1(c), onpolyethyleneterephthalate fibres clear blue needles are obtained whichare distinguished a by outstanding fastness to light, thermofixation,sublimation, rubbing, and washing, with high dye yield and very goodbuild. The cyclic5-nitro-2-phenylsulphonyl-anthraquinone-1.4-disulphonimide used asstarting material can be prepared for example by reaction of1.4-diamino-2- phenylsulphonyl-S-nitro-anthraquinone with oleum at 15-25 C. Instead of the cyclic disulphonimide, in the above example anequivalent amount of1.4-diamino-2-phe'nylsulphonyl-S-nitro-anthraquinone may be used, thecyclic disulphonimide then being formed in situ in the reaction withsulphur in oleum.

The dyes which are obtained from cyclic 5-nitro-2-arylsulphonyl-anthraquinone-l.4-disulphonimide according to Example 30,and their shades on polyethyleneterephthalate fibres, are given in thefollowing table:

phenylxulphonyl-anthraquinone.

Example Dye mixture consisting of Shade 381.4.5-tria1nino8-hydroxy-Z-(4'ethoxycarbonyl- Blue.

methyD-phenylsulphonyl-anthraquinone.

39 1.4.5 triamino-8-hydroxy-2-(3-ethoxycarbonyl)- Do.

phenylsulphonyl-anthraquinone.

40 1.4.5-triamino-8-l1ydr0xy-2-(4-methoxycarbonyl)- Do.

phenylsulphonyl'anthraquinone.

41 1.4.5-triamino-8-hydroxy-2-(4-dimethylarnlno) Do.

phenylsulphonyl-anthraquinone.

42 1.4.5-triarnino-8-hydroxy-2-(4-phenylamino) D0.

phenylsulphonyl-anthraquinone.

43 l.4.5-triarnin-8-hydroxy-2-(25-dichloro)-phenyl- Do.

sulphonyl-anthraqninone.

44 1.4.5-triamino-8-hydroxy-2-(4inethylthio)-phenyl- Do.

sulphonyl-anthraquin0ne.%

45 1.4.5-triamin0-8-hydroxy-2-(24-diruethyl)-phenyl- Do.

sulphonyl-anthraquinono.

46 1.4.5-triamino-8-hydroxy-2-B-naphthylsulphonyl- D0.

anthraquinone.

47 1.4.5-triamino-El-hydroxy2-a-naphthylsulphonyl- Do.

anthraquinone.

EXAMPLE 48 11.1 parts flowers of sulphur are added at 15-20 C. to amixture of 68 parts 65% oleum and 43 parts sulphuric acid monohydrate,the mixture stirred for 30 minutes at 1520 C. and then diluted with 167parts sulphuric acid monohydrate. 32.5 parts of a mixture of cyclic-nitro-2-and -3-methylsulphonyl-anthraquinone- 1.4-disulphonamide areintroduced at 20 C. and the mixture is stirred for 2 hours at 15-28 C.,warmed to 60 C. in 2 hours and heated to 90 C. in 1 hour. 67 parts 85%sulphuric acid are then added and the mixture is heated to 115 C. andafter 5 minutes at 115 C. allowed to cool. It is then diluted at 15-25C. with 150 parts water, filtered off from excess sulphur with suctionand the solution introduced into 1000 parts ice water. After the reddishblue amorphous product has been filtered off with suction, washed withwater and dried, 20.6 parts of a dye mixture consisting of1.4.5-triamino-8- hydroxy-2- and 3-methylsulphonyl-anthraquinone 89% ofthe theory) are obtained.

Analysis.-Calculated for C H N O S (347.3) (percent): N, 12.l; O, 23.05;S, 9.23. Found (percent): N, 11.91; 0, 23.28; S, 9.41.

Dyed or printed according to the process of Example 1*(b) or 1(c), thedye yields on polyethyleneterephthalate fibres clear blue shades whichare distinguished by very good fastness to light, thermofixation,sublimation, rubbing and washing, with high dye yield and very goodbuild.

The mixture of cyclic 5 -nitro-2- and-3-methylsulphonylanthraquinone-1.4-disulphonamide which is used asstarting mixture can be prepared for example as follows: 80 parts 32%sodium methanesulphinate are added at C. to 60 parts cyclicS-nitro-anthraquinone-1.4-disulphoni mide in 300 parts water and 11parts 98% sulphuric acid, the mixture heated to 6570 C. in about 1 hourand stirred at 6570 C. until the reaction is ended. After the mixturehas cooled, the product which has precipitated in yellow crystals isfiltered 011 with suction, washed with water and, after drying, 70 partsof a mixture of cyclic 5-nitro-2- and -3-methylsulphonyl-anthraquinone-1,4-disulphonamide (=97.5% of the' theory) are obtained.

When, as starting material for the reaction with sulphur, in oleum,there are used instead of a mixture of cyclic 5-nitro-2- and-3-methylsulphonyl-anthraquinone 1.4- disulphonamide equivalent amountsof the corresponding 1.4-disulphonirnide, the same end product isobtained.

The dyes which are obtained from mixtures of cyclic 5-nitro2- and-3-alkylor aralkyl-sulphonyl-anthraquinone-1.4-disulphonamides or-1.4-disulphonimides according to Example 48, and their shades onpolyethylene terephthalate fibres, are given in the following table:

E-ample Dye mixture consisting oi Shade 49 1.4.E-triamino-S-hydroxy-Z-and '3ethylsulph0nyl- Blue.

anthraquinone.

50 1.4.5-triamino-8-hydroxy-2- and -3-propylsulphonyl- Do.

anthraquinone.

51 1.4.5-triamino-8-hydroxy-2 and -3-isobutylsulphonyl- Do.

anthraquinone.

52 1.4.5-triamino-8-hydroxy-2- and -3-hexylsulphonyl- D0.

anthraquinone.

53 1.4.5-triamino-8-hydroxy2- and -3-(3-methyl)-cyclo- Do.

hexylsulphonyl-anthraquinone.

54 1.4.5-triamino-8-hydroxy-2- and -3-5-chlorobutyl- Do.

sulphonyl-anthraquinone.

55 1.4.5-triarnino-8-liydr0xy-2- and -3-chloromethy1- Do.

sulphonyl-anthraquinone.

56 1.4.5-triamino-8-hydroxy-2- and -3-;3-bromethyl- Do.

sulphonyl anthraquinone.

57 1.4.5-triamino-8-hydroxy-2- and -3- 3-methoxyethyl- D0.

sulphony1-anthraquinone.

58 1.4.S-triamino-S-hydroxy-2- and -3-B-(w-methoxy- Do.ethyleneoxyethylsulphonyl)-anthraquinone.

59 1.4.5-triamino-8-hydroxy-2- and -3-B-ethoxyethyl- Do.

sulphonyl-antl1raquinone.

60 1.4.5-trian1ino-8-hydroxy-2- and 43-5- cyanoethyl- Do.

sulphonyl-anthraquinone.

61 1.4.5-triamino-8-hydroxy-2- and -3-ethoxycarbonyl- Do.

methylsulphonyl-anthraquinone.

62 1.4.5-triamino-8-hydroxy-2- and -3-B-methoxy- Do.

carbonylethylsulphonyl-anthraquinone.

63 1.4.5-triarnino-S-hydroxy2- and -3-B-dimethylamino- Do.

ethylsulphonyl-anthraquinone.

64 1.4.5-triamino-8-hydroxy-Z- and -3-fi-diethylamiuo- D0.

ethylsulphonyl-anthraquinone.

65 1.4.5triamino-8-hydroxy-2- and -3-N-B-b1smeth0xy- Do.

ethylaminoethylsulphonyl-anthraquinone.

6ti 1.4.5-triarnino-8-hydroxy-2- and -3-NB-biscyano- D0.

ethylaminoethylsulphohyl-anthraquinone.

67 1.4.5-trian1ino-8-hydroxy-2- and -3-benzylsulphonyl- Do.

anthraquinone.

d8 1.4.fi-triaminoS-hydroxy-2-and -3-(4-chl0ro)-benzyl- Do.

sulphonyl-anthraquinone.

60 1.4.fi-triamino-S-hydroxy-Z- and -3B-naphthyl- Do.

methylsulphonylanthraquinone.

EXAMPLE 70 11.1 parts flowers of sulphur are added at 1520 C. to amixture of 68 parts 65% oleum and 43 parts sulphuric acid monohydrate,the mixture stirred for 30 minutes at 1520 C. and then diluted with 167parts sulphuric acid monohydrate. 32.5 parts cyclic S-nitro-2-inethylsulphonyl-anthraquinone-1.4-disulphonimide are now introducedat 15-20 C., the mixture stirred at 25- 28 C. for 2 hours, warmed to 60C. in 2 hours and heated to C. in 1 hour. 67 parts 85% sulphuric acidare then added, the mixture heated to C. and then diluted at 15-20 C.with parts water. After being filtered off from excess sulphur withsuction, the solution is slowly diluted at 15-25 C. with water until thereaction product has precipitated in small orange-red crystals. Byfiltering off with suction, washing with water and drying, 19.2 parts1.4.5-triamino-8-hydroxy-2-n1ethylsulphonyl-anthraquinone (=83% of thetheory) are obtained in the form of small blue crystals.

Analysis.--Calculated for C H N O S (347.3) (percent): N, 12.l; O,23.05; S, 9.23. Found (percent): N, 11.95; 0, 23.2];S, 9.48.

Dyed or printed according to the process of Example 1(b) or 1(c), thedye yields on polyethyleneterephthalate fibres clear blue shades whichare distinguished by very good fastness to light, thermofixation,sublimation, rubbing and washing, with high dye yield and very goodbuild.

The cyclic S-nitro-Z-methylsulphonyl-anthraquinone- 1.4-disulphonimideused as starting material can be prepared for example by reaction of1.4-diamino-2-methylsulphonyl-S-nitro-anthraquinone with oleurn at 1520C. Instead of the cyclic disulphonimide, in the above example anequivalent amount of 1.4-diamino-2-methylsulphonyl-S-nitro-anthraquinonemay be used, the cyclic disulphonimide then being formed in situ in thereaction with sulphur in oleum.

The dyes which are obtained from cyclic 5-nitro-2- alkylor-aralkylsulphonyl-anthraquinone 1,4-disulphon- Example Dye mixtureconsisting of- Shade 71 1.4.5triamino-8-hydroxy-Z-ethylsulphonyl- Blue.

anthraquinone.

72 1.4.5-t1'iamin08-hydr0xy-2-pr0pylsu1phonyl- D anthraquinone.

73-. 1.4.5triamino8-hydroxy-2 (4-methyl)-cyclohexyl- Do.

sulphonyl-anthraquinone.

74- 1.4.5-triaminO-S-hyd1'0xy-2-A-ch10robutylsulphonyl- D0.

anthraquinone.

75 1.4.5-triamino-8-hydroxy-2-ehl0romethylsuphonyl- D0.

anthraquinone.

76 l.4.5-triaminO-Shydroxy-Z-fi-bromoethylsulphonyl- D0.

anthraquinone.

77 1.4.5t1'iamino-8-hydroxy-2-B-oyanoethylsulphonyl- Do.

anthraquinone.

78 1.4.5-triamino-8-hydr0xy-2-ethoxyearbonylmethyl- D0.

sulphonyl-anthraquinone.

79 1.4.5-triamino-8-hydroxy-2-fl-methoxyearbonylethyl- D0.

sulphonyl-enthraquinone. i

80 1.4.5-triamin0-8-hydroxy-2- -methoxyethylsul- D0.

phonyl-anthraquinone.

81 1.4.5-triamino-8-hydroxy-2-B-dimethylamin0ethyl- Do.

sulphonyl anthraquinone.

82 1.4.Mriamino-S-hydroxy-Z-benzylsulphonyl- D0.

anthraquinone.

83 1.4.5-triamino-8-hydroxy-2-(4'-chloro)-benzy1sul- Do.

phonyl-anthraquinone.

84 1.4.5-triamino-8-hydroxy-2-B-naphthylmethylsul- D0.

phonyl-anthraquinone.

EXAMPLE 85 37.7 parts cyclic5-nitro-2.3-bis-methylsulphonyl-anthraquinone-l.4-disulphonamide arereacted with sulphur in oleum according to Example 1(a) and afterworking up as described thereinl.4.5-triamino-8-hydroxy-2.3-bismethylsulphonyl-anthraquinone isobtained as blue powder.

Dyed or printed according to the process of Example 1(b) or 1(c), thedye yields on polyethyleneterephthalate fibres reddish blue shades whichexhibit very good fastness to light, thermofixation, sublimation,rubbing and washing.

The dyes which are obtained from appropriate 2.3- disubstituted cyclicS-nitro-anthraquinone-l.4-disulphonamides or -1,4-disulphonimidesaccording to Example 1(a), and their shades on polyethyleneterephthalatefibres, are given in the following table:

pl1onyl-3-ethylsulphinyl-anthraquinone.

EXAMPLE 1 0 O 35.6 parts cyclic S-nitro-2-phenylthio-anthraquinone-1.4-disulphonimide are reacted with sulphur in oleum according to Example1(a) and after working up as described therein1.4.S-triamino-8-hydroxy-2-phenylthio-anthraquinone is obtained as bluepowder. Dyed or printed according to the process of Example 1(b) or1(0), the dye yields on polyethyleneterephthalate fibres clear, blueshades which exhibit excellent fastness to light, thermofixation,sublimation, rubbing and washing, with high dye yield and very goodbuild.

The dyes which are obtained from cyclic 5-nitro-2-aryl-, alkyloraralkylthio-anthraquinone-1.4-disulphonimides or -1,4-desulphonamidesaccording to Example 1(a), and their shades onpoly-ethyleneterephthalate fibres, are given in the following table:

Example Dye mixture consisting of Shade 1011.4vS-triamino-B-hydroxy-Z-(4-chloro)-phenylthio- Blue anthraquinone.

102 .1 1.4.5-triamino-8-hydroxy-2-(4-brom0)-phenylthio- D0.

anthraquinone.

103 1.4.5-triamino-8-hydroxy-2-(4-methyl)-phenylthio- D0.

anthraquinone.

104 1.4.5-triamin0-8hydr0xy-2-(3-methyl)-pheny1thio- Do.

anthraquinone.

105 1.4.fi-triamindS-hydroxy-Z-(4-t-butyl)-phenylthio D0.

anthraquinone.

106 1.4.5-triamin0-8-hydroxy-2-(4-methoxy-methyl)- Do.

phenylthio-anthraquinone.

107 1.4.5-triamino-8-hydroxy-2-(4-ehloromethyl)- Do.

phenylthioenthraquinone.

108 1.4.S-triamino-8-hydroxy-2-(4-ethoxy-carbonyl- Do.

methyl)-phenylthio-anthraquinone.

109 1.4.5-triamino-8-hydroxy2-(4-methoxy-earb0nyl)- D0.

phenylthio-anthraquin0ne.

110 1.4.5-triamino-8-hydroxy-2-(3-ethoxy-carbonyl)- D0.

phenylthio-anthraquinone.

111 1.4.5-triamino-8-hydr0xy-2-(4-dimethyl-amino- Do.

phenylthio-anthraquinone.

112 1.4.fi-triamino-8-hydroxy-2-methylthio-anthra- Do.

quinone 113 1.4.5 triarnino-8-hydroxy-2-ethylthi0-anthra Do.

quinone.

114 1.4.5-triamino-8-hydroxy-2-propylthio-anthra- D0.

quinone.

115 1.4.5-triamin0-8-hydr0xy-2-(3-methyl) D0.

eye10hexylthioanthraquinone.

116 1.4.5-triamino-8-hydroxy-2-l3-methoxyethylthio- D0.

anthraquinone.

117 1.4.5-triamino8-hydroxy-2-fi-ethoxyethylthio- D0.

anthraquinone.

118 1.4.5-triarnino-8-hydroxy-2-w-methoxy-fl- Do.

ethyleneoxyethylthi0-anthraquin0ne.

119 1.4.5-triamino-B-hydroxy-Z-B-cyanoethylthio- D0.

anthraquinone.

120.. 1.4.5-triamino-8-hydroxy-2-fl-methoxy-carbonyl- D0.

ethylthio-anthraquinone.

121 1.4.5-triamin0-8-hydroxy-Z-ethoxycarbonyl- D0.

methylthio-anthraquinone.

122 1.4.5-triamin0-8-hydroxy-2-fl-dimethylamin0- Do.

ethylthio-anthraquinone.

123 1.4.5-triamin0-8l1ydr0xy-2-benzylthio-anthra- Do.

quinone.

124 1.4.5-triamin0-8-hydroxy-2-(4-chl0r0)-benzylthio- D0.

anthraquinone.

125 1.4.5-triamino-8-hydroxy-2-(3-brorno)-phenylthio- Do.

anthraquinone.

EXAMPLE 126 45.2 parts cyclic S-nitro-Z,3-bis-(4-methylphenylthio)-anthraquinone-1.4-disulphonamide are reacted with sulphur in oleumaccording to Example 1(a) and after Working up as described therein1.4.5-triamin0-8-hydroxy-2.3- bis-(4'-methylphenylthio)-anthraquinone isobtained as reddish blue powder. Dyed or printed according to theprocess of Examples 1(b) or 1(0), the dye yields, onpolyethyleneterephthalate fibres, reddish blue shades which exhibit verygood fastness to light, thermofixation, sublimation, rubbing andwashing.

The dyes Which are obtained from appropriate 2.3- disubstituted cyclicS-nitro-anthraquinone-l.4-disulphonamides or -1.4-disu1phonimidesaccording to Example 1(a), and their shades on polyethyleneterephthalatefibres, are given in the following table:

36.8 parts cyclic 5-nitro-2-phenylsulphinyl-anthraquinone-1.4-disulphonimide are reacted with sulphur in oleum acording toExample 1(a) after working up as described therein1.4.5-triamino-8-hydroxy 2 phenylsulphinyl-anthraquinone is obtained asblue powder. Dyed or printed according to the process of Example 1(b) or1(c), the dye yields on polyethyleneterephthalate fibres clear blueshades which are distinguished by very good fastness to light,sublimation, thermofixation, rubbing and washing.

The dyes which are obtained from appropriately 2- substituted or2.3-disubstituted S-nitro-anthroquinone-l.4- disulphonamides or -1.4disulphonimides according to Example 1(a), and their shades onpolyethyleneterephthalate fibres, are given in the following table:

Example Dye mixture consisting of Shade 1391.4.5-triamino-8-hydroxy-2-(4-chlor0) Blue.

phenylsulphinyl-anthraquinone.

140 1.4.5-triamino-S-hydroxy-2-(4-methyl)- Do.

phenylsulphinyl-anthraquinone.

141 1.4.5-triamino-8-hydroxy-2-(4-rneth0xy- Do.

carbonyl)-phenylsulphinyl-anthraquinone.

142 1.4.5triamin0-8-hydroxy-2-(4-methoxy- Do.

methyl)-phenylsulphinylaiithraquinoi1e.

143 1.4.5-triamino-8-hydr0xy-2-methylsulphinyl- Do.

anthraquinone.

144 1.4.S-triamino-B-hydroxy-2-ethylsulphinyl- D0.

anthraquinone.

145 1.4.5-triamino-S-hydroxy-2-B-meth0xy- D0.

ethylsulphinyl-anthraquinone.

146 1.4.5-triamino-8-hydr0xy-2-wrneth0xy-B- D0.

ethyleneoxyethylsulphinyl-anthraquinone.

147 1.4.5-triamino-8l1ydroxy-Z-Bcyanoethyl- Do.

sulphinyl-anthraquinone.

148 1.4.5-triamino-S-hydroxy-Z-ethoxy-earbonyl- Do.

methylsulphinyl-anthraquinone.

149 1.4.5-triamino-8-hydr0xy2-methoxy- D0.

earbonylethylsulphinyl-anthraquinone.

150 1.4.5triamin0-8hydrOxy-Z-fl-(limethyl- Do.

ethylaminoethylsuophinyl-anthraquinone.

151 1.4.5-triamino-8 hydroxy-2-benzylsulphinyl- D0.

anthraquinone.

152 1.4.5-triamino-8-hydroxy-2.3-bis-(phenyl Reddish blue.

sulphinyD-anthraquinone.

153 1.4.5-triamino-8-hydr0xy-2-phenylsul- D0.

phinyl-3-methylsulphinyl-anthraquinone.

154 1.4.5-triarnino8-hydroxy-2.3bis-methyl- Do.

sulphinyl-anthraquinone.

155 1.4.fi-triamjno-B-hydroxy-Z-phenylsulpliinyl- D0.

3-br0mo-anthraquinone.

156 1.4.5triamin0-8l1ydr0xy-2-phenylsul- Do.

phinyl-E-chloro-anthraquinone.

157 1.4.5-triamino-8hydroxy-2methyl Do.

sulphinyl-3-br0mo-anthraquinone.

158 1.4.5-triarnino-8-hydroxy-2-meehyl- D0.

sulphinyl-3-chloro-anthraquinone.

159 1.4.5-triamino-8-hydroxy-2-phenyl- D0.

sulphinyl-3 ethylthio-anthraquinone.

160 1.4.5-triamin08-hydroxy-2-methyl- D0.

sulphinyI-S-phenylthio-anthraquinone.

EXAMPLE 1 61 22.2 parts flowers of sulphur are added at 1520 C. to amixture of 136 parts 65% oleum and 86 parts sulphuric acid monohydrate,the mixture stirred for 30 minutes at 15-20" C, and then diluted with334 parts sulphuric acid monohydrate. 68.8 parts cyclic 5-nitro-2-phenoxy-anthraquinone-l.4-disulphonimide are now introduced at 1520 C.;the mixture is stirred for 2 hours at 2528 C., heated to 60 C. in 2hours and then to C. in 1 hour. 134 parts 85% sulphuric acid are thenadded, the mixture heated to C., and after 5 minutes at 115 C. allowedto cool. It is then diluted with 200 parts water, filtered off fromprecipitated sulphur with suction and the solution introduced into 2000parts ice water. After the reddish blue amorphous product has beenfiltered off with suction, washed with water and dried, 44.3 parts1.4.S-triamino-8-hydroxy-2-phenoxy-anthraquinone (=89% of the theory)are obtained.

Dyed or printed according to the process of Example 1(b) or 1(c), thedye yields on polyethyleneterephthalate fibres clear blue shades whichare distinguished by outstanding fastness to light, thermofixation,sublimation,

rubbing and washing, with high dye yield and very good build.

The dyes which are obtained from cyclic 5-nitr0-2-aryloxy-anthraquinone-1.4-disulphonimides or -1.4-disulphonamidesaccording to Example 161, and their shades on polyethyleneterephthalatefibres, are given in the following table:

Example Dye mixture consisting of Shade 1621.4.5-triamino-8-hydroxy-2-(4-ehloro)-phenoxy- Blue.

anthraquinone.

163. 1.4.5-triamino-8hydroxy-2-(3-bromo)-phenoxyanthraquinone.

164 1.4.5-triamin0-8-hydroxy-2-(3-fluor0)pl1en0xy- Do.

anthraquinone.

165 1.4.5-triamino-8-hydroxy-2-(4-methyl)-pl1enoxy- Do.

anthraquinone.

166 1.4.5-triamin0-8hydroxy-2-(4-t-butyl)-phenoxy- Do.

anthraquinone.

167 1 .4.5-triamin0-8-hydroxy-2- (3-triflu0r0-methyl)- D0;

phenoxy-anthraquinone.

168 1.4.5-triamino-8-hydroxy-2-(4-methoxy-methyl)- Do.

phenoxy-anthraquinone.

169 1.4.5-triamino-8-hydroxy-2-(4-ethoxy-methyl)- Do.

phenoxy-anthraquinone.

170 1.4.5-triamino-8-hydroxy-2-(4-methoxy-ethyl)- Do.

phenoxy-anthraquinone.

171 1.4.5-triamino-8-hydroxy-2-(4-ehloro-rnethyl)- Do.

phenoxy-anthraquinone.

172 1.4.5-triamino-8-hydroxy-2-(4'-ethoxy-carbonyl- D0;

methyl)-phenoxy-anthraquin0ne.

173 1.4.S-triamino-S-hydroxy-Z-(3-ethoxy-carbonyl)- Do;

phenoxy-anthraquinone.

174 1.4.fi-triamino-S-hydr0xy-2-(4-methoxy-carb0nyl)- Do;

phenoxy-anthraquinone.

175 1.4.5-triamino-8-hydroxy-2(4-dimethyl-amino)- D0;

phenoxy-anthraquinone.

176 1.4.5-triamino-8-hydroxy-2-(2.5-dichloro)-phenoxy- D0;

anthraquinone.

177 1.4.5-triamino-8hyd.roxy-2-(2.4-dimethyl)-phenoxy Do;

anthraquinone.

178 1.4.5-triamino-8-hydroxy-Z-B-naphthoxy-anthraquin- Do.

one.

179 1.4.5-triamino-8-hydr0xy-2-a-naphthoxy-anthra- Do;

quinone.

180 1.4.5-triamino-8-hydroxy-2-(4-methylthio)-phenoxy- D0.

anthraquinone.

181 1.4.5-triamino'8-hydroxy-2-(4-methylsulphonyl)- D0;

phenoxy-anthraquinone.

EXAMPLE 182 75.3 parts cyclic 5-nitro-2-methoxy-anthraquinone-1.4-disulphonimide are reacted with sulphur in oleum according to Example161 and after working up as described therein 1.4.5triamino-8-hydroxy-2-methoxy-anthraquinone is obtained as reddish bluepowder. Dyed or printed according to the process of Example 1(b) or 1(c)the dye yields on polyethyleneterephthalate fibres clear blue shadeswhich are distinguished by very good fastness to light, sublimation,thermofixation, rubbing and washing.

The dyes which are obtained from cyclic S-nitro-alkoxyor-aralkoxy-anthraquinone-1.4-disulphonirnides or -1.4- disulphonamidesaccording to Example 161, and their shades on polyethyleneterephthalatefibres, are given in the following table:

Example Dye mixture consisting oi Shade 1831.4.5-triamino-8-hydroxy-2-ethoxy-anthraqulnone. Blue.

184 1.4.5-triarnino-8-hyd1-oxy 2-propoxyanthraqulnone Do.

185 1.4.S-triamin8-hydroxy-2-isobutoxy-anthraquinone- Do.

186 1.4.5-triamino-8-hydroxy-2-cye1ohexyloxy-anthra- Do.

quinone.

187 1.4.5-triamino-8-hydroxy-2-B-methoxy-ethyleneoxy- Do.

anthraquinone.

188 1.4.S-triamino-8 hydroxy-2-fl-ethoxy-ethyleneoxy Do.

anthraquinone.

189. 1 .4.5-triamino-B-hydroxy-2-w-meth oxy-B-ethyleneoxy- Do.

ethyleneoxy'anthraquinone.

100 1.4.fi-triamino-8-hydroxy-2-ethoxyearb onylmethoxy- D 0.

anthraquinone.

191. 1.4.5-triamino-8-hydroxy-l-B-methoxycarbonylene- Do.

oxy-antlrraquinone.

192 1.4.5-triamin0-8-hydroxy-2-B-di1ncthylaminoethylcne- Do.

city-anthraquinone.

193 1.4.5-triamino-8-hydr0xy-2-B-diethylamino- D0.

ethyleneoxy-anthraquinone.

194 1.4.5-1;riamino-B-hydroxy-2-B-bis-(methoxyethyl)-aminoethyleneoxy-anthraquinone.

195 1.4.5-triamino-8-hydroxy-2-fl-bis (eyanoethyD- Do.

aminoethyleneoxy-anthraquinone.

196 1.4.fi-triaminQ-S-hydroxy-Z-benzy1oxyanthraquinone D0.

197 1.4.5-triamino-8-hydroxy-2-(4-ehloro)-benzyloxy- Do.

anthraquinone.

198 1.4.Mriamino-S-hydroxy 2a-naphthylrnethoxy- D0.

anthraquinone.

199 1.4.fi-triamino-8-hydroxy-2-B-naphthylmethoxy- D0.

anthraquinone.

EXAMPLE 200 81.5 parts cyclic-nitro-2.3-bis-(phenoxy)-anthraquinone-1.4-disulphonimide are reactedwith sulphur in oleum according to Example 161 and after working up asdescribed therein 1.4.5-triamino-8-hydroxy-2.3-bis-(phenoxy)-anthraquinone is obtained as blue powder. Dyed or printedaccording to the process of Example 1(b) or 1(c), the dye yields onpolyethyleneterephthalate fibres blue shades which are distinguished byvery good fastness to light, sublimation, thermofixation, rubbing andwashing.

The dyes which are obtained from appropriately23- disubstitutedS-nitro-anthraquinone 1.4-disulphonimides and -1.4-disulphonamidesaccording to Example 161, and their shades on polyethyleneterephthalatefibres, are given in the following table:

eneoxy)-anthraquinone.

What we claim is: 1. Dyes of the formula wherein X stands for S0 R foran alkyl group containing up to 6 carbon atoms which may be substitutedby chlorine or bromine or lower alkoxy groups wherein R standsfurthermore for benzyl, chlorobenzyl or naphthylmethyl and wherein Rstands furthermore for a phenyl or naphthyl group or a phenyl groupsubstituted by halogen, lower alkyl, lower alkoXy lower alkyl,carboxylic lower alkyl ester groups, dilower alkyl amino group the akylgroups of which may be substituted by lower alkoxy groups or cyanogroups or wherein the phenyl may be substituted by lower alkyl mercaptogroups or the trifluoromethyl group; and wherein R further may stand formethylcyclohexyl, cyanomethylphenyl, ethoxycarbonylmethylphenyl,phenoxyphenyl, aminophenyl, phenylaminophenyl, cyano ethyl, methoxyethyleneoxy ethyl, dimethylamino ethyl, diethylamino ethyl,bis-methoxyethylamino ethyl, bis-cyanoethylamino ethyl,ethoxycarbonylmethyl, methoxycarbonylethyl;

R represents hydrogen, halogen, OR, -SR",

SO or R and R" represents a lower alkyl group which may be substitutedby alkoxy groups and wherein R represents furthermore phenyl and whereinR represents furthermore a benzyl group.

2. 1.4.5 triamino 8 hydroxy 2 phenylsulphonylanthraquinone.

3. 1.4.5 triamino 8 hydroxy 2 (4'-ch1oro)-phenylsulphonyl-anthraquinone.

4. 1.4.5 triamino 8 hydroxy 2 methylsulphonylanthraquinone.

5. 1.4.5 triamino 8 hydroxy 2 ethylsulphonyl.

anthraquinone.

References Cited UNITED STATES PATENTS Anthraceme und die Anthrachinon,Leipzig, Germany: Georg Thieme Berlag, p. 322-328 (1929).

LORRAINE A. WEINBERGER, Primary Examiner E. I SKELLY, Assistant ExaminerUS. Cl. X.R.

Patent No.

Inventor(s) Dated January 19 1971 RUTGER NEEFF,WILHELM GOHRBANDT, ROBERTKUTH ET It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Column Line Error "4-isopropyl," should be ---3-isopropyl-,-

"3-carboethoxy..." should be --3-carbethoxy...--.

" phenylthia)" should be -phenylthio)--.

"1,4" should be 1.4

"at" should be ---of.

"dlmethyl" should be --dimethyl---.

"phenylxulphonyl" should be -phenylsulphonyl-.

"anthraquinon" should be anthraquinone.

"desulphonamides" should be ---disulphonamides CERTIFICATE OF CORRECTIONPatent No. 3,557,154 Dated January 19, 1971 Inventor(s) RUTGER NEEFF,WILHELM GOHRABNDT, ROBERT KUTH ET It is certified that error appears inthe above-identified patent and that said Letters Patent are herebycorrected as shown below:

Column Line Error 11 Ex. 132 methoxycarboxylmethylthio should b e-methoxycarbonylmethy1thio-- ll 26 acording should be -according--.

13 Ex. 191 methoxycarbonyleneoxy should be --methoxycarbonylethyleneoxy13 Ex. 207 "Do. should be ---reddish blue-- 13 Ex. 211 "Do." should beblue 14 6 "-12 should be R' Signed and sealed this 19th day of October1971.

( EAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTI'SCHALK Attesting Officer ActingCommissioner of Pa

